Electron beam curable resin composition, resin frame for reflectors, reflector, semiconductor light emitting device, and method for producing molded body

ABSTRACT

Provided are an electron beam curable resin composition including polymethylpentene, and a crosslinking agent, in which the crosslinking agent has a saturated or unsaturated ring structure, at least one atom among atoms forming at least one ring is bonded to any allylic substituent of an allyl group, a methallyl group, an allyl group through a linking group, and a methallyl group through a linking group, and a molecular weight is 1,000 or less, a resin frame for reflectors using the resin composition, a reflector, and a molding method using the resin composition.

TECHNICAL FIELD

The present invention relates to an electron beam curable resincomposition, a resin frame for reflectors, a reflector, a semiconductorlight emitting device, and a method for producing a molded body.

BACKGROUND ART

In the related art, as a method for mounting an electronic component ona substrate, a method (a reflow method) in which an electronic componentis temporarily fixed to a predetermined position of a substrate to whichsolder is attached in advance, the substrate is then heated by means ofinfrared light, hot air, or the like to melt the solder, and anelectronic component is fixed has been adopted. It is possible toincrease the mounting density of the electronic component on the surfaceof the substrate by the method.

However, the electronic component which has been used in the related arthas insufficient heat resistance and particularly, in a reflow processusing infrared heating, a problem that the surface temperature of thecomponent increases locally, or the like arises. Thus, there has been ademand for a resin composition and an electronic component havingfurther excellent heat resistance.

In addition, since an LED element as a semiconductor light emittingdevice has a small size, a long life, and excellent power savingperformance, LED elements have been widely used as a light source of adisplay lamp, or the like. In recent years, an LED element having higherbrightness has been produced at a relatively low cost, and thus, the useof LED elements as a light source in place of a fluorescent lamp and alight bulb has been considered. When LED elements are used as such alight source, a method has been frequently used in which plural LEDelements are arranged on a surface mounting type LED package, that is, ametal substrate (LED mounting substrate) of aluminum or the like, and areflector (a reflecting body) which reflects light in a predetermineddirection is arranged in the vicinity of each LED element to obtain highilluminance.

However, since LED elements give off heat generation during lightemitting, in an LED light device adopting such a method, the reflectoris deteriorated due to a rising temperature during light emitting of theLED elements, and the reflectivity is degraded and brightness isdegraded. Thus, the lifetime of the LED element is shortened.Accordingly, heat resistance is required for the reflector.

In order to respond to the requirement of the heat resistance, in PTL 1,a polymer composition which is used in a reflector of a light emittingdiode is proposed and specifically, a polymer composition includingpolyphthalamide, carbon black, titanium dioxide, glass fibers, and anantioxidant is disclosed. The reflectivity of the composition ismeasured after the composition undergoes heat aging. The composition hassatisfactory reflectivity with less yellowing compared to a polymercomposition not including carbon black.

In addition, in PTL 2, a thermosetting light reflecting resincomposition using an optical semiconductor device in which an opticalsemiconductor element and wavelength converting means such as afluorescent substance are combined is disclosed.

CITATION LIST Patent Literature

[PTL 1] PCT Japanese Translation Patent Publication No. 2006-503160

[PTL 2] Japanese Unexamined Patent Application Publication No.2009-149845

SUMMARY OF INVENTION Technical Problem

However, the heat aging test of the thermosetting light reflecting resincomposition disclosed in PTL 2 is performed under a more practicalcondition of 150° C. for 500 hours for verification. However, themolding time is 90 seconds, which is longer than a molding time of athermoplastic resin, and post-curing at 150° C. for 2 hours is required.Thus, there is a problem in productivity.

The heat aging test of the polymer composition disclosed in PTL 1 is anevaluation for a short period of time of 3 hours at 170° C., and thus,whether or not satisfactory results in heat resistance and durabilitycan be obtained under the practical condition for a longer period oftime is not clear.

From the above, an object of the present invention is to provide anelectron beam curable resin composition which can exhibit excellent heatresistance in the reflow process and can exhibit excellent heatresistance even when being formed into a molded body such as areflector, a resin frame for reflectors using the resin composition, areflector, a semiconductor light emitting device, and a molding methodusing the resin composition.

Solution to Problem

As the result of intensive studies to achieve the above object, thepresent inventor has been found that the object can be achieved by thefollowing inventions. That is, the present invention is as follows.

[1] An electron beam curable resin composition including:polymethylpentene; and a crosslinking agent, wherein the crosslinkingagent has a saturated or unsaturated ring structure, at least one atomamong atoms forming at least one ring is bonded to any allylicsubstituent of an allyl group, a methallyl group, an allyl group througha linking group, and a methallyl group through a linking group, and amolecular weight is 1,000 or less.

[2] The electron beam curable resin composition according to [1],wherein at least two atoms among the atoms forming one ring of thecrosslinking agent are each independently bonded to the allylicsubstituent.

[3] The electron beam curable resin composition according to [2],wherein the ring of the crosslinking agent is a six-membered ring, atleast two atoms among the atoms forming the ring are each independentlybonded to the allylic substituent, and another allylic substituent isbonded to an atom in a meta position with respect to an atom bonded withone allylic substituent.

[4] The electron beam curable resin composition according to any one of[1] to [3], wherein the crosslinking agent is expressed by the followingFormula (1).

(In the Formula (1), R¹ to R³ are each independently any allylicsubstituent of an allyl group, a methallyl group, an allyl group throughester bonding, and a methallyl group through ester bonding.)

[5] The electron beam curable resin composition according to any one of[1] to [3], wherein the crosslinking agent is expressed by the followingFormula (2).

(In the Formula (2), R¹ to R³ are each independently any allylicsubstituent of an allyl group, a methallyl group, an allyl group throughester bonding, and a methallyl group through ester bonding.)

[6] The electron beam curable resin composition according to any one of[1] to [5], wherein 0.1 parts by mass to 15 parts by mass of thecrosslinking agent is blended with respect to 100 parts by mass ofpolymethylpentene.

[7] The electron beam curable resin composition according to any one of[1] to [6], further including a white pigment.

[8] The electron beam curable resin composition according to [7],further including inorganic particles other than the white pigment.

[9] The electron beam curable resin composition according to [8],wherein the inorganic particles other than the white pigment arespherical fused silica particles and/or modified cross-section glassfibers.

[10] A resin frame for reflectors including: a cured product of theelectron beam curable resin composition according to any one of [1] to[9].

[11] The resin frame for reflectors according to [10], wherein athickness is 0.1 mm to 3.0 mm.

[12] A reflector including: a cured product of the electron beam curableresin composition according to any one of [1] to [9].

[13] A semiconductor light emitting device including: an opticalsemiconductor element; and a reflector which is provided in the vicinityof the optical semiconductor element and reflects light from the opticalsemiconductor element in a predetermined direction, wherein the opticalsemiconductor element and the reflector are provided on a substrate, andat least a part of the light reflecting surface of the reflector iscomposed of a cured product of the electron beam curable resincomposition according to any one of [1] to [9].

[14] A method for producing a molded body including: an injectionmolding process of performing injection molding on the electron beamcurable resin composition according to any one of [1] to [9] at aninjection temperature of 200° C. to 400° C. and at a mold temperature of20° C. to 100° C.; and an electron beam irradiation process ofperforming electron beam irradiation treatment before and after theinjection molding process.

Advantageous Effects of Invention

According to the present invention, it is possible to provide anelectron beam curable resin composition which can exhibit excellent heatresistance in a reflow process and can exhibit excellent heat resistanceeven when being formed into a molded body such as a reflector, a resinframe for reflectors using the resin composition, a reflector, asemiconductor light emitting device, and a molding method using theresin composition.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic cross-sectional view showing an example of asemiconductor light emitting device of the present invention.

FIG. 2 is a schematic cross-sectional view showing an example of thesemiconductor light emitting device of the present invention.

DESCRIPTION OF EMBODIMENTS

[1. Electron Beam Curable Resin Composition]

An electron beam curable resin composition of the present inventionincludes polymethylpentene and a specific crosslinking agent.

The refractive index of polymethylpentene is 1.46, and this value isvery close to the refractive index of a silica particle. Thus, it ispossible to suppress inhibition of optical properties such astransmittance and reflectivity even when polymethylpentene is mixed.Considering this point, for example, the curable resin composition issuitably used as a reflector of a semiconductor light emitting device.

However, heat resistance was not sufficient in a reflow process in somecases. To solve this problem, in the present invention, a resincomposition exhibiting a sufficient heat resistance even in a reflowprocess can be obtained by containing a specific crosslinking agent inpolymethylpentene and irradiating the resin with an electron beam.Accordingly, even when the resin composition is formed into a reflector,it is possible to prevent the reflector from being deformed by meltingof the resin.

Polymethylpentene has properties of having a high melting point of 232°C., not being decomposed even at a processing temperature of about 280°C., and having a decomposition temperature close to 300° C. On the otherhand, since organic peroxides and photopolymerization initiators havingsuch properties are not generally present, crosslinking by the organicperoxides and crosslinking by ultraviolet light are not possible.

In addition, even when polymethylpentene is irradiated with an electronbeam (for example, absorbed radiation dose: 200 kGy), molecular chainsare cut simultaneously with the crosslinking, and thus, effectivecrosslinking does not occur only by the resin. However, since aneffective crosslinking reaction occurs through electron beam irradiationby containing the crosslinking agent according to the present invention,it is possible to prevent deformation by melting of the resin even in areflow process.

Such a crosslinking agent has a saturated or unsaturated ring structure,and at least one atom among atoms forming at least one ring is bonded toany allylic substituent of an allyl group, a methallyl group, an allylgroup through a linking group, and a methallyl group through a linkinggroup. By containing the crosslinking agent having such a structure,satisfactory electron beam curability is exhibited and thus, a resincomposition having excellent heat resistance can be formed.

Examples of the saturated or unsaturated ring structure include a cycloring, a hetero ring, and an aromatic ring. The number of atoms formingthe ring structure is preferably 3 to 12, more preferably 5 to 8, and a6-membered ring is still more preferable.

In addition, the molecular weight of the crosslinking agent according tothe present invention is 1,000 or less, preferably 500 or less, and morepreferably 300 or less. When the molecular weight is more than 1,000,the dispersibility in the resin composition is deteriorated and thus, aneffective crosslinking reaction cannot occur even when the resin isirradiated with the electron beam.

Further, the number of the ring structures is preferably 1 to 3, morepreferably 1 or 2, and still more preferably 1.

Here, examples of the linking group of the crosslinking agent accordingto the present invention include ester bonding, ether bonding, analkylene group, and a (hetero)allylene group. An atom that is not bondedto the allylic substituent among the atoms forming the ring is bondedwith hydrogen, oxygen, nitrogen, and the like, or is bonded with varioussubstituents.

In the crosslinking agent according to the present invention, it ispreferable that at least two atoms among the atoms forming one ring ofthe crosslinking agent are each independently bonded to the allylicsubstituent. When the ring structure is a 6-membered ring, it ispreferable that at least two atoms among the atoms forming the ring areeach independently bonded to the allylic substituent, and with respectto an atom to which one the allylic substituent is bonded, anotherallylic substituent is bonded to an atom in a meta position.

Further, it is preferable that the crosslinking agent according to thepresent invention be expressed by the following Formula (1) or (2).

(In the Formula (1), R¹ to R³ are each independently any allylicsubstituent of an allyl group, a methallyl group, an allyl group throughester bonding, and a methallyl group through ester bonding.)

(In the Formula (2), R¹ to R³ are each independently any allylicsubstituent of an allyl group, a methallyl group, an allyl group throughester bonding, and a methallyl group through ester bonding.)

Examples of the crosslinking agent expressed by the above Formula (1)include trially isocyanurate, methyl diallyl isocyanurate, diallylmonoglycidyl isocyanuric acid, monoallyl diglycidyl isocyanurate, andtrimethallyl isocyanurate.

Examples of the crosslinking agent expressed by the above Formula (2)include orthophthalic acid diallyl ester, and isophthalic acid diallylester.

The amount of the crosslinking agent blended according to the presentinvention is preferably 0.1 parts by mass to 15 parts by mass, morepreferably 0.5 parts by mass to 5 parts by mass, and still morepreferably 0.1 parts by mass to 2.5 parts by mass with respect to 100parts by mass of polymethylpentene. By blending 0.1 parts by mass to 15parts by mass of the crosslinking agent, crosslinking can proceedeffectively without bleed-out.

As the polymethylpentene resin, a homopolymer of 4-methylpentene-1 ispreferable. However, the polymethylpentene resin may be a copolymer of4-methylpentene-1 and other α-olefin, for example, α-olefin having 2 to20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene,1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene,1-eicocene, 3-methyl-1-butene, or 3-methyl-1-pentene, or may be acopolymer mainly including 4-methylpentene-1 containing 90 mol % or moreof 4-methyl-1-pentene.

Regarding the molecular weight of the homopolymer of 4-methylpentene-1,the weight average molecular weight Mw in terms of polystyrene, measuredby gel permeation chromatography, is 1,000 or more, and particularlypreferably 5,000 or more.

It is preferable that the electron beam curable resin composition of thepresent invention include a white pigment. By including the whitepigment, the resin composition can be used for a reflector or the like.In addition, it is preferable that the resin composition includeinorganic particles other than the white pigment. Examples of theinorganic particles other than the white pigment include spherical fusedsilica particles, modified cross-section glass fibers “Flat Fiber™”, andother glass fibers, and spherical fused silica particles and/or modifiedcross-section glass fibers are preferable. Such an electron beam curableresin composition is particularly suitable for a reflector.

As the white pigment according to the present invention, titanium oxide,zinc sulfide, zinc oxide, barium sulfide, potassium titanate, and thelike can be used singly or in a mixture. Among them, titanium oxide ispreferable. The content of the white pigment is preferably 5 parts bymass to 200 parts by mass, more preferably 10 parts by mass to 150 partsby mass, and still more preferably 20 parts by mass to 80 parts by mass,with respect to 100 parts by mass of polymethylpentene resin.

In consideration of formability, and from the viewpoint of obtaininghigh reflectivity, the average particle size of the white pigment ispreferably 0.10 μm to 0.50 μm, more preferably 0.10 μm to 0.40 μm, andstill more preferably 0.21 μm to 0.25 μm in a primary particle sizedistribution. The average particle size can be obtained as an averagemass value D50 in particle size distribution measurement by a laser beamdiffraction method.

The spherical fused silica particles and the modified cross-sectionglass fibers according to the present invention can be blended withtypical thermoplastic resin compositions and thermosetting resincompositions such as epoxy resin, acryl resin, and silicone resin, andthe resultants can be used singly or in a mixture.

Here, the term of “spherical” of the “spherical fused silica particles”does not refer to a fibrous shape such as glass fibers, a shape having alarge unevenness difference, and a flaky shape having a thin thickness,but refers to a shape in which the longest distance and the shortestdistance between the center and the surface are almost the same.Specifically, the term of “spherical” refers to a substantiallyspherical shape or a spherical shape in which the following averagesphericity is 0.8 or more. Since the spherical fused silica particleshave a substantially spherical shape or a spherical shape, the particlesare not anisotropic and are highly fillable. In addition, fluidity to amold, mold wear resistance, and the like are excellent.

The average sphericity can be measured by performing image analysis of aparticle image imaged by using, for example, a scanning electronmicroscope “FE-SEM, Model JSM-6301F” manufactured by Nippon ElectronicsCo., Ltd. That is, a projected area (A) and peripheral length (PM) of aparticle are measured from the resulting image. When an area of acomplete circle corresponding to the peripheral length (PM) is (B), thecircularity of the particle can be indicated as A/B. Assuming a completecircle having the same peripheral length as the peripheral length (PM)of the sample particle, since PM=2πr and B=πr², the expression ofB=π×(PM/2π)² is established. Thus, the sphericity of each particle canbe calculated as sphericity=A/B=A×4π/(PM)². The thus obtained sphericityof 200 arbitrary particles is calculated and an average value thereof isused as an average sphericity of powder. Among commercially availableproducts, products having “a spherical shape” have an average sphericityof 0.8 or more.

For example, the spherical fused silica particles are produced through aprocess of injecting a silicon dioxide powder raw material (for example,silica stone powder) from a burner into a flame formed in a melting zoneinside a furnace in a powder state to accompany a carrier gas such asair. Generally, commercially available products can be used.

The volume average particle size of the spherical fused silica particlesis preferably 0.1 μm to 500 μm, more preferably 1 μm to 200 μm, andstill more preferably 5 μm to 150 μm from the viewpoint of the balancebetween heat resistance and formability. The volume average particlesize can be obtained as an average mass value D50 in particle sizedistribution measurement by a laser beam diffraction method.

In addition, the “modified cross-section glass fibers” refer to fibershaving a cross-sectional shape in which a minor axis and a major axis ofthe cross section are different. Since an almost equal degree ofreinforcement can be made in a resin flow direction (MD) and a verticaldirection (TD) thereof, the fiber is excellent in warpage prevention ofa molded product.

In the present invention, the glass fibers are preferably glass fibershaving a cross sectional shape in which the minor axis D1 of the crosssection is 0.5 μm to 25 μm, the major axis D2 is 0.6 μm to 300 μm, and aratio D2/D1 of D2 relative to D1 is 1.2 to 30, and an average fiberlength of 0.75 μm to 300 μm. The fiber size and the fiber length can beobtained in such a manner that a predetermined amount of glass fibersare randomly extracted from an arbitrary point of a glass fiberlaminated body, the extracted fibers are pulverized with a mortar, orthe like, and the resultant is measured by an image processingapparatus.

The content of the spherical fused silica particles and/or the modifiedcross-section glass fibers is preferably 10 parts by mass to 300 partsby mass, more preferably 30 parts by mass to 200 parts by mass, andstill more preferably 50 parts by mass to 120 parts by mass with respectto 100 parts by mass of the polymethylpentene resin.

The electron beam curable resin composition of the present invention canbe prepared by mixing the aforementioned polymethylpentene resin and thecrosslinking agent with at least any inorganic particles selected fromthe spherical fused silica particles, the modified cross-section glassfibers, and other glass fibers, and the white pigment, as required, atthe aforementioned predetermined ratio. As for the mixing method, knownmeans such as stirrers such as a two-roll mill, a three-roll mill, ahomogenizer, and a planetary mixer, and melt kneading machines such as aPolylab system, and a Labo Plastomill can be applied. The aforementionedmeans may be used under any condition of room temperature, a cooledstate, a heated state, normal pressure, a decompressed state, and apressurized state.

As long as the effect of the present invention is not impaired, variousadditives can be added. For example, for the purpose of improving theproperties of the resin composition, various additives such as whiskers,silicone powders, thermoplastic elastomers, organic synthetic rubbers,internal releasing agents such as fatty acid ester, glyceric acidesters, zinc stearate, and calcium stearate, antioxidants such asbenzophenone-based antioxidants, salicylic acid-based antioxidants,cyanoacrylate-based antioxidants, isocyanurate-based antioxidants,anilide oxalate-based antioxidants, benzoate-based antioxidants,hindered amine-based antioxidants, benzotriazole-based antioxidants, andphenol-based antioxidants, and light stabilizers such as hinderedamine-based light stabilizers and benzoate-based light stabilizers canbe blended.

By using the electron beam curable resin composition of the presentinvention, various molded bodies can be molded and a thin molded body(for example, a reflector) having a thinner thickness can be prepared.

Such a molded body is preferably produced by a molding method of thepresent invention. That is, the molded body is preferably prepared by amolding method including an injection molding process of performinginjection molding on the electron beam curable resin composition of thepresent invention at a cylinder temperature of 200° C. to 400° C. and amold temperature of 20° C. to 100° C., and an electron beam irradiationprocess of performing electron beam irradiation treatment before andafter the injection molding process.

As long as formability is not impaired, a crosslinking reaction byelectron beam irradiation can be performed before the molding.

The acceleration voltage of the electron beam can be appropriatelyselected depending on a resin and a thickness of the layer to be used.For example, when a molded product has a thickness of about 1 mm,typically, an uncured resin layer is preferably cured at an accelerationvoltage of about 250 kV to 2,000 kV. In the electron beam irradiation,the higher the acceleration voltage is, the higher the transmissioncapacity is. Thus, when a base material which is deteriorated by theelectron beam is used as a base material, the acceleration voltage isselected so that the transmission depth of the electron beam becomessubstantially equal to the thickness of the resin layer, and thus,excessive electron beam irradiation to the base material can besuppressed and deterioration of the base material by the excessiveelectron beam can be minimized. In addition, the absorbed radiation dosewhen the resin is irradiated with the electron beam is appropriatelyselected depending on the constitution of the resin composition.However, a dose in which the crosslinking density of the resin layer issaturated is preferable, and the dose is preferably 10 kGy to 400 kGy,and more preferably 50 kGy to 200 kGy. Further, the electron beam sourceis not particularly limited. For example, various electron beamaccelerators such as a Cockcroft-Walton accelerator, a van de Graaffaccelerator, a resonance transformer accelerator, an insulated coretransformer accelerator, a linear accelerator, a dynamitron accelerator,and a high frequency accelerator can be used.

Such an electron beam curable resin composition of the present inventioncan be applied to various uses as a composite material obtained byapplying and curing the resin composition on a base material or a curedproduct of the electron beam curable resin composition. For example, theresin composition can be applied to a heat resistant insulating film, aheat resistant release sheet, a heat resistant transparent basematerial, a light reflecting sheet of a solar cell, lighting such asLED, and a light source reflector for a television.

[2. Resin Frame for Reflectors]

A resin frame for reflectors of the present invention is made of a curedproduct obtained by molding the aforementioned electron beam curableresin composition of the present invention. Specifically, the resin forreflectors of the present invention is used as a pellet, and is formedinto a resin frame having a desired shape by injection molding toproduce a resin frame for reflectors of the present invention. Thethickness of the resin frame for reflectors is preferably 0.1 mm to 3.0mm, more preferably 0.1 mm to 1.0 mm, and still more preferably 0.1 mmto 0.5 mm.

Using the electron beam curable resin composition of the presentinvention, a thinner resin frame can be prepared compared to a resinframe, for example, using glass fiber whose shape is anisotropic.Specifically, a resin frame having a thickness of 0.1 mm to 3.0 mm canbe produced. In addition, even when the thickness of the thus moldedresin frame for reflectors of the present invention is reduced, warpagecaused by including an anisotropic filler such as a glass fiber does notoccur, and thus, shape stability and handleability are excellent.

When an LED chip is mounted on the resin frame for reflectors of thepresent invention, and further the resin frame is sealed with a knownsealing agent, and subjected to die bonding so as to have a desiredshape, the resin frame can be used as a semiconductor light emittingdevice. The resin frame for reflectors of the present invention acts asa reflector, and also functions as a frame for supporting thesemiconductor light emitting device.

Foaming caused by water is suppressed in the process of producing theframe by containing the spherical fused silica particles in the resinframe for reflectors of the present invention compared to a case inwhich porous silica particles are blended, and thus, micropores smallenough to cause a defect are not formed. Accordingly, in a product usingthe frame (for example, a semiconductor light emitting element), adefect caused by the micropores does not easily occur and thus, thedurability of the product can be improved.

[3. Reflector]

A reflector of the present invention is made of a cured product obtainedby curing the aforementioned electron beam curable resin composition ofthe present invention.

The reflector may be used in combination with a semiconductor lightemitting device, which will be described later, or may be used incombination with a semiconductor light emitting device (a substrate formounting LED) made of another material.

The reflector of the present invention has an action of mainlyreflecting light from an LED element of a semiconductor light emittingdevice to a lens (a light emitting portion). Details of the reflectorare the same as the details of a reflector (a reflector 12 which will bedescribed later) applied to the semiconductor light emitting device ofthe present invention, and thus, the description thereof will beomitted.

Foaming caused by water is suppressed in the process of producing thereflector by containing the spherical fused silica particles in thereflector of the present invention, and thus, micropores small enough tocause a defect are not formed. Accordingly, in a product using thereflector (for example, a semiconductor light emitting element), adefect caused by the micropores does not easily occur and thus, thedurability of the product can be improved.

As described above, in a semiconductor light emitting element in which areflector is formed using the electron beam curable resin compositioncontaining the spherical fused silica particles, micropores small enoughto cause a defect in the reflector are not formed, and thus, a defectcaused by the micropores does not easily occur. Therefore, thedurability of the product can be improved.

[4. Semiconductor Light Emitting Device]

As shown in FIG. 1, a semiconductor light emitting device of the presentinvention includes an optical semiconductor element (for example, an LEDelement) 10, and a reflector 12 which is provided in the vicinity of theoptical semiconductor element 10 and reflects light from the opticalsemiconductor element 10 to a predetermined direction, and the opticalsemiconductor element and the reflector are provided on a substrate 14.Then, at least a part of the light reflecting surface of the reflector12 (the entire surface in FIG. 1) is made of a cured product of theaforementioned reflector composition of the present invention.

The optical semiconductor element 10 is a semiconductor chip (a lightemitting body) which emits radiated light (UV or blue light in the caseof a white light LED, in general) and has a double-hetero structure inwhich an active layer formed of, for example, AlGaAs, AlGaInP, GaP orGaN, is interposed between n-type and p-type clad layers, and is shapedin the form of, for example, a hexahedron, each side having a length ofabout 0.5 mm. In the case in which the LED element is mounted by wirebonding, the LED element is connected to an electrode (not shown) (aconnecting terminal) through a lead wire 16.

The shape of the reflector 12 depends on the shape of the end portion(junction portion) of a lens 18 and is typically cylindrical or annularsuch as square-shaped, circular-shaped, and ellipse-shaped. In theschematic cross-sectional view of FIG. 1, the reflector 12 iscylindrical (annular). The entire end surface of the reflector 12 is incontact with and fixed to the surface of the substrate 14.

The inner surface of the reflector 12 may be tapered so as to extendupward in order to increase the degree of directivity of light from theoptical semiconductor element 10 (refer to FIG. 1).

Further, when the end portion of the reflector 12 close to the lens 18is processed into a shape according to a shape of the lens 18, thereflector 12 can function as a lens holder.

As shown in FIG. 2, only the light reflecting surface of the reflector12 may be used as a light reflecting layer 12 a made of the electronbeam curable resin composition of the present invention. In this case,the thickness of the light reflecting layer 12 a is preferably 500 μm orless, and more preferably 300 μm or less, from the viewpoint of loweringheat resistance. A member 12 b in which the light reflecting layer 12 ais formed can be made of known heat resistant resin.

As described above, the lens 18 is provided on the reflector 12. Thelens 18 is typically made of a resin and can be formed into a variety ofstructures according to the purpose, the application and the like andmay be colored.

A space portion which is formed by the substrate 14, the reflector 12,and the lens 18 may be a transparent sealing portion or a gap portion asrequired. The space portion is usually a transparent sealing portionfilled with a material that provides translucency and insulationproperties or the like. With the space portion, it is possible toprevent electrical failures caused when, in wire-bonding mounting, thelead wire 16 is disconnected, cut or short-circuited from the connectionportion with the optical semiconductor element 10 and/or the connectionportion with the electrode due to a force applied by direct contact tothe lead wire 16 and a vibration, an impact and the like appliedindirectly. Additionally, it is possible not only to protect the opticalsemiconductor element 10 from moisture, dust and the like but also tomaintain reliability for a prolonged period.

Examples of the material (a transparent sealant composition) thatprovides translucency and insulation properties generally include asilicone resin, an epoxy silicone resin, an epoxy-based resin, anacryl-based resin, a polyimide-based resin, a polycarbonate resin andthe like. Among them, a silicone resin is preferable in terms of heatresistance, weather resistance, low contraction and resistance todiscoloration.

An example of a method for producing the semiconductor light emittingdevice shown in FIG. 1 will be described below.

First, the reflective resin composition of the present invention ismolded into the reflector 12 having a predetermined shape by transfermolding, compression molding, injection molding, or the like using amold having a cavity space of a predetermined shape. Then, the opticalsemiconductor element 10, electrode, and lead wire 16 preparedseparately are fixed to the substrate 14 by an adhesive or a joiningmember, and further, the reflector 12 is fixed to the substrate 14.Subsequently, a transparent sealant composition including a siliconeresin and the like is injected into a recess portion formed by thesubstrate 14 and the reflector 12, cured by heating, and drying to forma transparent sealing portion. Then, the lens 18 is arranged on thetransparent sealing portion to obtain the semiconductor light emittingdevice shown in FIG. 1.

After the lens 18, is placed in a state where the transparent sealantcomposition is not cured, the composition may be cured.

EXAMPLES

Next, the present invention will be described in more detail usingexamples, but the present invention is not limited to these examples.

Materials used in Examples 1 to 15 and Comparative Examples 1 to 12 areas follows.

(A) Resin

Polymethylpentene resin: TPX RT18 (manufactured by Mitsui Chemicals,Inc., molecular weight: MW 500,000 to 600,000)

Cyclic polyolefin copolymer resin: COC APL6015 (manufactured by MitsuiChemicals, Inc., glass transition temperature: 145° C.)

Polybutylene terephthlate resin: Novaduran 5008 (manufactured byMitsubishi Engineering-Plastics Corporation, intrinsic viscosity [η]=0.9dl/g, melting temperature: 224° C.)

(B) Crosslinking Agent

The crosslinking agents are as follows. In addition, crosslinking agentsin which the structure can be specified among the following crosslinkingagents are shown in Tables 1-1 and 1-2 and shown by the chemicalformulae below.

Crosslinking agent 1: DAP monomer (orthophthalic acid diallyl ester),manufactured by DAISO CO., LTD.

Crosslinking agent 2: DAP 100 monomer (isophthalic acid diallyl ester),manufactured by DAISO CO., LTD.

Crosslinking agent 3: TRIC (trially isocyanurate), manufactured byNippon Kasei Chemical Co., Ltd.

Crosslinking agent 4: MeDAIC (methyl diallyl isocyanurate), manufacturedby SHIKOKU CHEMICALS CORPORATION

Crosslinking agent 5: DA-MGIC (diallyl monoglycidyl isocyanuric acid),manufactured by SHIKOKU CHEMICALS CORPORATION

Crosslinking agent 6: MA-DGIC (monoallyl diglycidyl isocyanurate),manufactured by SHIKOKU CHEMICALS CORPORATION

Crosslinking agent 7: TMAIC (trimethallyl isocyanurate), manufactured byNippon Kasei Chemical Co., Ltd.

Crosslinking agent 8: RICON 153 (polybutadiene), manufactured bySartomer Company Inc.

Crosslinking agent 9: RICON 154 (polybutadiene), manufactured bySartomer Company Inc.

Crosslinking agent 10: RICON 157 (polybutadiene), manufactured bySartomer Company Inc.

Crosslinking agent 11: TAIL prepolymer (trially isocyanurateprepolymer), manufactured by Nippon Kasei Chemical Co., Ltd.

Crosslinking agent 12: TEPIC (1,3,5-trisglycidyl isocyanuric acid),manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.

Crosslinking agent 13: TEPIC-PAS (mixture of 1,3,5-trisglycidylisocyanuric acid and phthalic anhydride), manufactured by NISSANCHEMICAL INDUSTRIES, LTD.

Crosslinking agent 14: 1,3,5-tris(2-carboxyethyl) isocyanurate acrylate

Crosslinking agent 15: M315 (ED-modified isocyanurate triacrylate),manufactured by Toagosei Chemical Industries, Co., Ltd.

Crosslinking agent 16: DPHA (dipentaerythritol hexaac rylate),manufactured by Nippon Kayaku Co., Ltd.

TABLE 1-1 Crosslinking agent and co- crosslinking agent (molecularStructure weight) Formula R¹ R² R³ Crosslinking agent 1 DAP monomer(246.3) Formula (2)

— Crosslinking agent 2 DAP 100 monomer (246.3) Formula (2)

—

Crosslinking agent 3 TAIC (249.3) Formula (1)

Crosslinking agent 4 MeDAIC (223.2) Formula (1) CH₃

Crosslinking agent 5 DA-MGIC (265.3) Formula (1)

Crosslinking agent 6 MA-DGIC (281.3) Formula (1)

Crosslinking agent 7 TMAIC (291.4) Formula (1)

TABLE 2 Crosslinking agent and co- crosslinking agent (molecularStructure weight) Formula R¹ R² R³ Crosslinking agent 8 RICON 153(4,700) Formula (3) Having polybutadiene skeleton and large number ofallyl groups present Crosslinking agent 9 RICON 154 (5,200) Formula (3)Having polybutadiene skeleton and large number of allyl groups presentCrosslinking agent 10 RICON 157 (1,800) Formula (3) Having polybutadieneskeleton and large number of allyl groups present Crosslinking agent 11TAIC Prepolymer (3,000 or more) Large number of ring structuresexpressed by Formula (1) present Crosslinking agent 12 TEPIC (297)Formula (1)

Crosslinking agent 13 TEPIC-PAS Formula (1)

Crosslinking agent 14 CIC acid acrylate (639.6) Formula (1)

Crosslinking agent 15 M315 (423) Formula (1)

Crosslinking agent 16 DPHA (578) Formula (4) —

Formulae (1) to (4) showing structures in Tables 1-1 and 1-2 are asfollows.

(C) Inorganic Particle

Modified cross-section glass fiber “Flat Fiber™”: CSG 3PA-820(manufactured by Nitto Boseki Co., Ltd., fiber length: 3 mm)

(D) White Pigment

Titanium oxide particles: PF-691 (manufactured by Ishihara SangyoKaisha, Ltd., rutile-type structure, average particle size: 0.21 μm)

(E) Additive

Silane coupling agent: KBM-303 (manufactured by Shin-Etsu Chemical Co.,Ltd.)

Releasing agent: SZ-2000 (manufactured by Sakai Chemical Industry Co.,Ltd.)

Antioxidant: IRGANOX 1010 (manufactured by BASF Japan Ltd.)

Processing stabilizer: IRGAFOS 168 (manufactured by BASF Japan Ltd.)

Examples 1 to 15, and Comparative Examples 1 to 12

Various materials were mixed and kneaded to obtain resin compositions asshown in Tables 2, 3, and 4. Here, the kneading was performed using aPolylab system (batch type biaxial kneader).

These compositions were press-molded under the condition of 250° C. for30 seconds at 20 MPa to have a size of 750 mm×750 mm and a thickness of0.2 mm, thereby preparing molded bodies.

The molded bodies were irradiated with an electron beam at anacceleration voltage of 250 kV with a predetermined absorbed radiationdose. The following properties of the molded bodies were evaluated. Theresults are shown in Tables 2, 3, and 4.

(Evaluation 1)

Storage Elastic Modulus

The storage elastic modulus of each molded sample was evaluated usingRSA III (manufactured by TA Instruments) under the conditions of ameasurement temperature of 25° C. to 300° C., a temperature rising rateof 5° C./rain, and a strain of 0.1%. The storage elastic modulus at 260°C. is shown in Tables 2 and 3 below.

(Evaluation 2)

Reflow Heat Resistance

Whether or not each molded sample was deformed was evaluated through asmall nitrogen atmosphere reflow apparatus RN-S (manufactured byPanasonic Electric Works Co., Ltd.) which was set such that the maximumtemperature of the sample surface was retained at 260° C. for 10 secondsbased on a dimensional change rate (a sum of a change rate in a verticaldirection and change rate in a horizontal direction). The results areshown in Table 4 below.

(Evaluation 3)

Long-term Heat Resistance

The light reflectivity was measured at a wavelength of 230 nm to 780 nmusing a spectroscopic photometer UV-2550 (manufactured by ShimadzuCorporation) before and after each molded sample was left at 150° C. for24 hours and 500 hours. In Table 4, the results at a wavelength of 450nm are shown.

Table 2 Example 1 2 3 4 5 6 7 Material Resin Parts 100 100 100 100 100100 100 blending by mass Crosslinking Type Crosslinking CrosslinkingCrosslinking Crosslinking Crosslinking Crosslinking Crosslinking agentagent 1 agent 2 agent 3 agent 4 agent 5 agent 6 agent 7 Parts 2 2 2 2 22 2 by mass Storage Electron 100 kGy Unmeasurable 128 143 158 104Unmeasurable Unmeasurable elastic beam modulus/ absorbed 200 kGyUnmeasurable 9 169 4 29 Unmeasurable Unmeasurable kPa radiation dose 400kGy 0.11 19 358 18 20 12 67 Comparative Example 1 2 3 4 5 6 7 8 9Material Resin Parts 100 100 100 100 100 100 100 100 100 blending bymass Crosslinking Type Crosslinking Crosslinking CrosslinkingCrosslinking Cross- Cross- Cross- Cross- Cross- agent agent 8 agent 9agent agent linking linking linking linking linking 10 11 agent 12 agent13 agent 14 agent 15 agent 16 Parts 2 2 2 2 2 2 2 2 2 by mass StorageElectron 100 Unmeasurable elastic beam kGy modulus/ absorbed 200Unmeasurable kPa radiation kGy dose 400 Unmeasurable kGy

TABLE 3 Comparative Example Example 8 9 10 11 12 13 10 Material ResinParts by mass 100 100 100 100 100 100 100 blending Crosslinking TypeCrosslinking agent 3 agent Parts by mass 0.5 1 2 3 5 10 0 StorageElectron  50 kGy Unmeasurable 22 60 80 155 213 Unmeasurable elastic beam100 kGy Unmeasurable 30 143 150 508 675 Unmeasurable modulus/ absorbed200 kGy 1 40 169 248 787 2270 Unmeasurable kPa radiation dose

TABLE 4 Comparative Example Example Composition (parts by mass) 14 15 1112 Material Resin Polymethylpentene TPX RT- 100 100 blending 18 Cyclicpolyolefin 100 copolymer APL6015 Polybutylene terephthlate 100 Novaduran5008 Crosslinking agent Crosslinking agent 3: TAIC 2 2 2 2 (triallyisocyanurate) Inorganic particle Modified cross-section 60 60 60 glassCSG 3PA-820 White pigment Titanium oxide PF-691 45 45 45 45 AdditivesKBM-303 1.5 1.5 1.5 1.5 SZ-2000 0.5 0.5 0.5 0.5 IRGANOX 1010 1 1 1 1IRGAFOS 168 0.5 0.5 0.5 0.5 Electron beam absorbed radiation dose 100100 100 100 (kGy) @ acceleration voltage 250 kV Evaluation Reflow heatDimensional Vertical + Horizontal 0.7%  0.1%  0.6%  0.3%  resultresistance change rate MAX 260° C. Long-term Reflectivity Initial* 96%95% 85% 94% heat @ 450 nm  24 h later 94% 92% 84% 92% resistance 500 hlater 86% 83% 76% 82% 150° C. *“Initial” means that before the sample isleft at 150° C.

As seen from Tables 2 and 3, when the resin composition of the presentinvention was irradiated with the electron beam under the presence of aspecific crosslinking agent, the resin composition was not melted evenin a high temperature range and the storage elastic modulus was able tobe obtained. Accordingly, it was confirmed that an effectivecrosslinking reaction proceeded by the electron beam irradiation underthe presence of a specific crosslinking agent.

From Table 3, it was confirmed that the storage elastic modulus alsoincreased as the amount of the crosslinking agent and the electron beamirradiation dose increased. Accordingly, it was confirmed that thedegree of crosslinking was dependent on the amount of the crosslinkingagent and the electron beam irradiation dose.

In a case of the resin composition only composed of resin and acrosslinking agent, when the amount of the crosslinking agent increased,press molding was not likely to be performed. However, press molding waspossible by blending inorganic particles or a white pigment with theresin composition.

From Table 4, it was confirmed that the deformation of the reflectingresin composition irradiated with the electron beam by the reflow testwas significantly reduced.

In addition, it was confirmed that long-term heat resistance wasexcellent. Particularly, comparing the results of Example 15 andComparative Examples 11 and 12 in which the types of the resins weredifferent, it was found that Example 15 exhibited the best dimensionalstability and long-term heat resistance.

As described above, the resin composition of the present invention isuseful for a reflector, and a reflecting material for semiconductorlight emitting devices.

REFERENCE SIGNS LIST

10 . . . Optical semiconductor element

12 . . . Reflector

14 . . . Substrate

16 . . . Lead wire

18 . . . Lens

The invention claimed is:
 1. A method for producing a reflectorcomprising: an injection molding process of performing injection moldingon an electron beam curable resin composition; and an electron beamirradiation process of performing electron beam irradiation treatmentbefore and after the injection molding process; wherein the electronbeam curable resin composition comprises: polymethylpentene and acrosslinking agent has a saturated or unsaturated ring structure, atleast one atom among atoms forming at least one ring is bonded to anyallylic substituent of an allyl group, a methallyl group, an allyl groupthrough a linking group, and methallyl group through a linking group,and a molecular weight is 1,000 or less.
 2. The method for producing thereflector according to claim 1, further comprising a white pigment. 3.The method for producing the reflector according to claim 2, furthercomprising inorganic particles other than the white pigment.
 4. Themethod for producing the reflector according to claim 3, wherein theinorganic particles other than the white pigment are spherical fusedsilica particles and/or modified cross-section glass fibers.
 5. Themethod for producing the reflector according to claim 1, wherein atleast two atoms among the atoms forming one ring of the crosslinkingagent are each independently bonded to the allylic substituent.
 6. Themethod for producing the reflector according to claim 5, wherein thering of the crosslinking agent is a six-membered ring, at least twoatoms among the atoms forming the ring are each independently bonded tothe allylic substituent, and another allylic substituent is bonded to anatom in a meta position with respect to an atom bonded with one allylicsubstituent.
 7. The method for producing the reflector according toclaim 1, wherein an injection temperature is 200° C. to 400° C. and amold temperature is 20° C. to 100° C.
 8. The method for producing thereflector according to claim 1, wherein the crosslinking agent isexpressed by the following Formula (1)

wherein in the Formula (1), R¹ to R³ are each independently any allylicsubstituent of an allyl group, a methallyl group, an allyl group throughester bonding, and a methallyl group through ester bonding.
 9. Themethod for producing the reflector according to claim 1, wherein thecrosslinking agent is expressed by the following Formula (2)

wherein in the Formula (2), R¹ to R³ are each independently any allylicsubstituent of an allyl group, a methallyl group, an allyl group throughester bonding, and a methallyl group through ester bonding.
 10. Themethod for producing the reflector according to claim 1, wherein 0.1parts by mass to 15 parts by mass of the crosslinking agent is blendedwith respect to 100 parts by mass of polymethylpentene.